CN102167926B - Novel nano cuprous oxide conductive ink and preparation method thereof - Google Patents

Abstract

The invention discloses a formula and a preparation method of ink for inkjet printing with nano-cuprous oxide conductive ink as the main conductive component. The novel nano-nano cuprous oxide conductive ink comprises: 5wt%-70wt% nano-cuprous oxide, 5wt%-70wt% colorant, 0-5wt% dispersant, 5wt%-25wt% ink carrier solvent. The method is as follows: mixing nanometer cuprous oxide, additives and ink carrier according to a certain ratio and order, and then ultrasonically dispersing, fully mixed and then sintered. The conductive ink for inkjet printing disclosed by the invention has good implementability, and the product has the characteristics of low cost, low resistance, adjustable viscosity, easy jetting and the like.

Description

A novel nano-cuprous oxide conductive ink and preparation method thereof

Technical field

The present invention relates to a conductive ink formula for inkjet printing and its preparation method, more specifically, relates to a high nano-metal content, high dispersibility, high electrical conductivity and adjustable viscosity with low cost and simple process Conductive ink composition and preparation method thereof.

Background technique

"Printable Electronics Technology" (Printable Electronics Technology) is a new cross-technology that has emerged as more and more printing technology cross-penetrates with other industry technologies. It is realized by the organic integration of printing technology and electronic technology. It is a new technology that makes various electronic circuits or devices on various substrates, especially flexible substrates, by printing technology, so that it has functions such as electronic transmission, signal emission, electromagnetic shielding, photoelectric conversion, etc., and adopts the additive method , High-speed printing technology to produce various electronic devices and circuits, compared with the previously commonly used photoetching subtractive method technology, has had a major impact on the economic and industrial structure of electronics manufacturers, and conductive ink is exactly the printing electronic material core components.

Nano-cuprous oxide has become another hot spot in the research of conductive inks because of its good chemical stability, high electrical conductivity, and low price compared with commonly used nano-silver. The publication number CN101089058 patent applied by Samsung Electric Co., Ltd. discloses a conductive ink composition for inkjet printing, which comprises: 30-85 parts by weight of metal nanoparticles, 10-60 parts by weight of solvent, 10 parts by weight - 30 parts by weight of a wetting agent consisting of a diol- or polyol-based compound, and 0.1-10 parts by weight of a diol-based ether compound additive for adjusting viscosity. The invention can adjust the viscosity of the ink to maintain a high concentration when using an inkjet printing device to form the lead. However, this invention has many formulas, and most of them are non-conductive components, which will definitely affect the conductivity of the final product when it is solidified to form a lead. In addition, the compatibility of the metal powder and the matrix is also a difficult problem for this invention, and the price is also very expensive. . Chinese patent CN1671805A discloses a conductive nano-ink with low sintering temperature and its preparation method, which discloses a new method for manufacturing conductive ink containing metal nano-powder. The formula of this invention is complicated, and it is also difficult to solve the problem of uniform conductivity. Chinese patent CN1354208 discloses a conductive ink composition, which is a kind of thermosetting conductive ink, which is used for through-hole connection or similar electrical or electronic applications to provide stable electrical connection. The invention uses epoxy resin as a carrier and copper, silver, etc. as conductive components. This method solves the problem of solvent volatilization, but its low electrical conductivity is its fatal flaw.

Contents of the invention

Aiming at the problems existing in the background technology, the present invention proposes a new type of conductive ink and its preparation method which is simple in process, fast and efficient, stable in conductivity, strong in operability, energy-saving and environment-friendly. A novel nano-cuprous oxide conductive ink described in the invention is characterized in that it includes 5%-70wt% nano-cuprous oxide, 5%-70wt% colorant, 0-5wt% dispersant, 5wt%-25wt% % ink carrier solvent;

The novel nano-cuprous oxide conductive ink is characterized in that: the nano-cuprous oxide is an oil-soluble nano-cuprous oxide, which can be a nano-cuprous oxide powder, or a dispersion liquid of a nano-cuprous oxide, or It is a composition of nano cuprous oxide powder and dispersion liquid, and its particle size is 2-50nm;

The novel nano-cuprous oxide conductive ink is characterized in that: the oil-soluble nano-cuprous oxide is nano-copper coated with a protective agent on the surface, and the protective agent can be dodecanoic acid, alkane alcohol, Alkanethiol, Sodium Dodecylbenzene Sulfonate, Dodecyltrimethylammonium Chloride, Cetyltrimethylammonium Bromide, Polyethylene Glycol, Polyvinylpyrrolidone (PVP), Polyvinyl Alcohol One or more of the protective agents;

Described a kind of novel nano-cuprous oxide conductive ink is characterized in that: coloring agent can be yellow pigment, magenta, also can be the composition of black pigment and magenta, the composition of magenta and yellow pigment, cyan and Composition of magenta pigment, composition of cyan and black pigment, composition of cyan and yellow pigment, the total amount of colorant accounts for 2wt% to 3wt% of the total amount of ink;

The novel nano-cuprous oxide conductive ink is characterized in that: the ink carrier solvent surfactant can be hexadecyldimethylammonium chloride (1631), octadecyltrimethylammonium chloride (1831), cationic guar gum (C-14S), cationic panthenol, cationic silicone oil, dodecyl dimethyl amine oxide (0B-2) and other cationic surfactants, can also be fatty alcohol polyoxyethylene ether Anionic surfactants such as sodium sulfate and sodium lauryl sulfate, amphoteric surfactants such as dodecyl dimethyl betaine, carboxylate imidazoline, etc., or alkyl alcohol amides (FFA) , fatty alcohol polyoxyethylene ether (AE), alkylphenol polyoxyethylene ether (APE or OP) and other nonionic surfactants, wherein the amount of surfactant added accounts for 0.1wt% to 1wt% of the total ink;

The novel nano-cuprous oxide conductive ink is characterized in that: the ink dispersant can be a silicate dispersant such as water glass, or sodium tripolyphosphate, sodium hexametaphosphate and sodium pyrophosphate, etc. Alkali metal phosphate dispersants can also be triethylhexyl phosphoric acid, sodium lauryl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide, gull gum, fatty acid polyethylene glycol esters and other organic Dispersants, wherein organic dispersants are preferred;

The ink carrier solvent is characterized in that: the ink carrier solvent can be toluene, xylene, or low polarity and nonpolarity of 6-18 alkane such as n-hexane, n-heptane, cyclohexane and its isomers Sexual solvent, wherein the solvent accounts for 5wt% to 25wt% of the total ink;

The novel nano-cuprous oxide conductive ink is characterized in that its surface tension is about 25mN/m-35mN/m, its viscosity is 1.5-2.0cP, and its conductivity is greater than 1S/cm;

The preparation method of described a kind of novel ink-jet printing conductive ink is characterized in that, it can comprise:

A: Dissolving the surfactant in the carrier solvent to prepare the ink carrier;

B: adding nano-cuprous oxide pigments to the ink carrier;

C: Add colorants and dispersants to the ink carrier;

After fully mixing, it can be dispersed by ultrasonic;

can also include

A: Dissolving the surfactant in the carrier solvent to prepare the ink carrier;

B: Add colorants and dispersants to the ink carrier;

C: adding nano-cuprous oxide pigments to the ink carrier;

After fully mixing, it can be dispersed by ultrasonic;

can also include

A: Dissolving the surfactant in the carrier solvent to prepare the ink carrier;

B: Mix the nano-cuprous oxide colorant and the non-silver colorant;

C: Add the mixed colorant and dispersant to the ink carrier;

After fully mixing, it can be dispersed by ultrasonic;

Any of the three mixing methods.

Beneficial effects of the present invention:

1. The invention has high nano-metal content, adjustable viscosity, high electrical conductivity and low product price;

2. The present invention has simple formula, simple production process, high production efficiency, strong operability, and is suitable for large-scale production;

3. The conductive ink nano-cuprous oxide prepared by the present invention has small particle size, narrow distribution and good stability;

4. The process cost of the present invention is low, the generation of harmful waste is less, and the energy consumption is less, which meets the modern requirements of "energy saving, environmental protection, and green production".

Description of drawings

The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

Fig. 1 is nano-cuprous oxide transmission electron microscope photo in conductive ink;

Figure 2 is the UV transmittance test of nano-cuprous oxide.

Table 1 is embodiment test result. Surface tension test: K12 surface tension meter produced by German Krüss company; viscosity/cP (60rpm): measured by NDJ-79 rotational viscometer produced by Shanghai Yiyou Instrument Co., Ltd.; conductivity test: produced by Mettler The model is S30K conductivity meter measurement.

Detailed ways

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application. The test results of the experimental products are also attached.

Example 1, first dissolve 0.1 part of octylphenol polyoxyethylene ether in 5 parts of n-hexane. Then add 70 parts of nano-cuprous oxide and stir evenly, then add 24.9 parts of yellow pigment and 0.5 part of dispersant water glass into the system while stirring, and mix evenly with ultrasound.

Example 2, first dissolve 0.1 part of octylphenol polyoxyethylene ether in 5 parts of n-hexane, then add 25 parts of pigment fuchsin, 0.5 part of dispersant sodium hexametaphosphate, stir evenly and add 70 parts of nano-cuprous oxide In the system, it can be mixed after sufficient ultrasonication.

Embodiment 3: 29 parts of pigment magenta, 1 part of dispersant sodium hexametaphosphate and 50 parts of nano cuprous oxide n-hexane dispersion are stirred and mixed, then dissolved with 0.5g polyoxyethylene sorbitan fatty acid ester In 19.5 parts of n-heptane, it can be dispersed evenly by ultrasonic.

Example 4: Dissolve 0.1 part of octylphenol polyoxyethylene ether and 1 part of sodium carboxymethylcellulose in 5 parts of n-hexane. Then add 60 parts of nano-cuprous oxide and stir evenly, then add 34.9 parts of yellow pigment into the system while stirring, and mix evenly by ultrasonic.

Example 5: first dissolve 0.5 parts of dodecyl dimethyl betaine in 25 parts of n-hexane, then add 3 parts of gull gum and 66.5 parts of pigment fuchsin successively, stir 5 parts of nano-cuprous oxide Add it to the system, and mix it with sufficient ultrasound.

Example 6: 70 parts of pigment magenta, 5 parts of dispersant gull gum and 15 parts of nano-cuprous oxide's n-hexane dispersion are stirred and mixed, and then 9.5 parts of 0.5 parts of dodecyl dimethyl betaine are dissolved In n-heptane, it can be dispersed evenly by ultrasonic.

Table 1: Example product test results

Surface tension/mN/m Viscosity/cP(60rpm) Conductivity/mS/cm Example 1 31 2.2 10.8 Example 2 31.5 2.0 11.5 Example 3 27 1.6 9.0 Example 4 30 1.7 9.8 Example 5 25 1.6 1.5 Example 6 29 1.8 4.2

Claims (7)

1. A novel nano-cuprous oxide conductive ink, characterized in that: (1) It includes 5wt% ~ 70wt% nano-cuprous oxide, 5wt% ~ 70wt% colorant, 0 ~ 5wt% dispersant, 5wt% ~ 25wt% ink carrier solvent; (2) Nano-cuprous oxide is a powder or dispersion of oil-soluble nano-cuprous oxide, or a composition of nano-cuprous oxide powder and a dispersion, and its particle size is 2-50nm; (3) Its surface tension is 25mN/m-35mN/m, its viscosity is 1.5-2.0cP, and its electrical conductivity is greater than 1mS/cm. the 2. A new type of nano-cuprous oxide conductive ink according to claim 1, characterized in that: the oil-soluble nano-cuprous oxide is nano-copper coated with a protective agent on the surface, and the protective agent is twelve to ten Octanoic acid, alkanol, alkanethiol, sodium dodecylbenzenesulfonate, dodecyltrimethylammonium chloride, cetyltrimethylammonium bromide, polyethylene glycol, polyvinylpyrrolidone (PVP), one or more of polyvinyl alcohol. the 3. a kind of novel nano-cuprous oxide conductive ink according to claim 1, is characterized in that: described coloring agent is yellow pigment, magenta, or the composition of black pigment and magenta, magenta and yellow pigment A combination of cyan and magenta pigments, a combination of cyan and black pigments, a combination of cyan and yellow pigments. the 4. a kind of novel nano-cuprous oxide conductive ink according to claim 1, is characterized in that: described ink carrier solvent surfactant is hexadecyl dimethyl ammonium chloride, stearyl trimethyl ammonium chloride, cationic guar gum, cationic panthenol, cationic silicone oil, dodecyl dimethyl amine oxide cationic surfactant, or fatty alcohol polyoxyethylene ether sodium sulfate, sodium lauryl sulfate anionic surface Active agent, or lauryl dimethyl betaine, carboxylate imidazoline amphoteric surfactant, or alkanolamide, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether nonionic surface Active agent, wherein the added amount of surfactant accounts for 0.1wt%-1wt% of the total amount of ink. the 5. a kind of novel nano-cuprous oxide conductive ink according to claim 1, is characterized in that: described ink dispersant is water glass silicate dispersant, or sodium tripolyphosphate, sodium hexametaphosphate and sodium pyrophosphate alkali metal phosphate dispersant, or triethylhexyl phosphate, sodium lauryl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide, guar gum, fatty acid polyethylene glycol Ester organic dispersant. the 6. A new type of nano-cuprous oxide conductive ink according to claim 4, characterized in that: the ink carrier solvent is toluene, xylene, or n-hexane, n-heptane, cyclohexane, 6-18 alkane Low polar and non-polar solvents and its isomers. the 7. the manufacture method of a kind of novel nano-cuprous oxide conductive ink according to claim 1, comprising: A1: Dissolve the surfactant in the carrier solvent to prepare the ink carrier; B1: Add nano-cuprous oxide to the ink carrier; C1: Add colorants and dispersants to the ink carrier; After fully mixing, it can be dispersed by ultrasonic; or include A2: Dissolve the surfactant in the carrier solvent to prepare the ink carrier; B2: Add colorants and dispersants to the ink carrier; C2: Add nano-cuprous oxide to the ink carrier; After fully mixing, it can be dispersed by ultrasonic; or include A3: Dissolving the surfactant in the carrier solvent to prepare the ink carrier; B3: Mix nano-cuprous oxide and colorant; C3: Add the above mixture and dispersant to the ink carrier; After fully mixing, it can be dispersed by ultrasonic; Any of the three mixing methods. the

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